Acid-treated borated oxazolines



i United States Patent Office 3,030,374 Patented Apr. 17, 1932 3,030,374ACID-TREATED BORATED OXAZOLINES Sarah H. Belden, Cleveland, Ohio,assignor to TheStan'dgd Oil Company, Cleveland, ()hio, a'corporation ofbio No Drawing. Original application'Feb. 25, 1959, Scr. No. 795,348,now Patent No. 2,993,765, dated July 25, 1961. Divided andthisapplication Dec. 30, 1959, Ser. No. 3,224

2 Claims. (Cl. 260- 307) This invention rel-ates to novelboroncompounds.

This application is a division of my application Serial No. 795,348,filed February 25, 1959, now Patent No. 2,993,765 granted 'June25, 1961.

.Co pendingapplication Serial No. 795,349, filed February 25, 1959, nowPatent No. 2,965,459, which is assigned-tomy assignee and of which Lam-aco-inventor, discloses a class of-novel borated oxazoline compounds foruse in gasoline which areiselected from the.group consisting of (1) and(2) H \C X I 1 OCH2 Hie-'0 wherein R represents an aliphatic'hydrocarbonradical containing 7 to '19 carbon atoms, where -n is a small wholenumber from 1 to 3,and Where R represents a radical selected from thegroup consisting o'f'hydrogen and a lower 'alkyl radical containing 1 to3 carbon atoms.

A gasoline containing small amounts of a boron compound selected fromthis group of compounds isdisclosed as offering improved "engineoperation,being=particularly effective in suppressing surface ignitionand in alleviating carburetor deposits and carburetor icing. These boroncompounds are particularly desirable for use as additives for gasolinebecause, in contradistinction to many other organo boron compounds, theyexhibit excellent stability toward hydrolysis in pure form and whendissolved in gasoline.

Any of the compounds having the general formula ofiered above aresuitable "for the present invention. The preferred compounds, however,are those in which R as defined heretofore contains 11 to 17 carbonatoms for maximum solubility "in hydrocarbon fuel and where R is theequivalent of 1R Mixtures of compounds may be used as R and thisfrequently will be the case since the R radical is derived fromnaturally occurring fats and oils, and hence R will correspond to thefatty acid radicals in such fats and oils, such as tallow, cottonseedoil, soybean oil, etc. The nature of R does not affect the resultsappreciably, it has been found, and therefore its selectionwill'bedictate'd'largly by=economics. The commercial grade 'of the compounds,including small amounts of impurities or .by-products, are suitable.

Furtherinformation as to the nature of these com- ,pounds, the'rnannerin whichthey'may be prepared, and

the benefits which may be derived from thegasolinein 'whichthey areincorporated maybe gained from said application Serial No. 795,349, andthe description-of 'said'application'Serial No. 795,349 isinc'orporatedherein "by reference to such an extent as is required for acomplete understanding of these compounds.

Ithas now been found that such borated oxazoline compounds may befurther improved for use'as a gasoline additive by further reaction withan acid. The

present invention is not to be limited to any particular theorywithirespect to the manner in which the acid adds to the borated ozazolinecompounds, butit is believed that'the acid coordinates with the nitrogenatom present inthe ozazoline ring resulting in the "formation "of asalt.

'ThepH of the'bo'rated oxazoline compound is' lowered almost immediatelyupon 'mixing at ambient temperature with the desired'amountof acid.Water of reaction may be formed in the reaction, depending upon the acidusedand'its form. In some instances -it will be desired to.remove thiswater before incorporating the 'additiveinto gasoline. "Where-it isdesiredto remove the water of reaction in the preparation,-the boratedoxazo- "line 'may' be'reacted with the acid inthe presence of a solventwhich azeotropes with water, such as benzene. The reaction'mixture'is'then refluxed at'the 'azeotropic distillation temperaturefor a time to efiect the removal of'the wa'ter'with the solvent.

The above acid-treated boron'compounds of this in- -venti'on may'beincorporated in gasoline in amounts bepreferred. The amount of the acidshould 'be'such as "to lower thepH value of the resulting product, asdetermined at 25% of the final product in benzene in accordance withtechniques described in ASTM-D664 54 from about 6.7 to a'range of from3L0 to 6:0, and preferably 3.3 to 95.7. The "choice of the'acid or acidsto be'used will, of course, be determined by economics,p'H'c'onfsiderations, "and by the performance benefits which "aredesired.

The-following examples are in no way intended to limit'the'invention butare'presented 'to typify the process 'ofthis acid 'additionto borated'oxazoline compounds of which Example A below'is exemplary, and toillustrate the reaction products that -are obtained thereby.

EXAMPLE A IOOKparts of 2-hept'adecenyl 4,4-bis-'(hydroxy methyl)oxazoline 'w'as dissolved in 200 partsofbenzene. 16.8

parts'of boric-aeid -wa's then added (a 1:1:molar ratio) and'the'mixture refluxed 'at the 'azeotropic distillation temperature forthe removal of water with the benzene overhead from the reactionmixture. The remainder of the benzene was distilled off. The reactionproceeds readily in accordance with the following equation:

The reaction product was a clear liquid upon cooling and was soluble ingasoline. Its pH was 6.7.

EXAMPLE 1 100 parts of borated Z-heptadecenyl 4,4-bis-(hydroxy methyl)oxazoline having the formula C H NBO as made in accordance with ExampleA, was reacted with 15.2 parts of acetic acid (a 1:1 molar ratio) in 200parts of benzene and refluxed at the azeotropic distillation temperaturefor several hours for the removal of water with the benzene. Uponcooling, the reaction product was clear and readily soluble in gasoline.The pH of the reaction product was 5.7.

EXAMPLE 2 100 parts of borated Z-heptadecenyl 4,4 bis-(hydroxy methyl)oxazoline having the formula C H NBO was reacted with'6.1 parts of P (a120.17 molar ratio) and 5 parts water in 200 parts of benzene andrefluxed at the azeotropic distillation temperature for two hours. Thereaction product upon cooling was clear and readily soluble in gasoline.The pH of the product was 4.2.

EXAMPLE 3 100 parts of borated Z-heptadecenyl 4,4-bis-(hydroxy methyl)oxazoline having the formula C H NBO was reacted with 16.1 parts ofoxalic acid dihydrate (a 1:0.5 molar ratio) in 200 parts of benzene andrefluxed at the azeotropic distillation temperature for several hoursfor the removal of water with benzene. The reaction product upon coolingwas clear and readily soluble in gasoline. The pH of the reactionproduct was 3.3.

The results in Table I below illustrate the improvement towardemulsification characteristics obtained with gasolines containing theacid-treated borated oxazoline compounds of this invention.

The results reported were obtained in accordance with aviation gasolinewater tolerance test as set forth in ASTM-D1094-53. In this test, 20 ml.of water is shaken with 80 ml. of gasoline in a graduated cylinder fortwo minutes at ambient temperature. The change of hydrocarbon level isthen observed. The lower the change of hydrocarbon volume, the lesstendency the gasoline has to emulsify with the water. In addition, inthe present test the cuff height, which normally appears as a distinctand cloudy layer between the hydrocarbon phase and the water phase, wasalso measured. The lower the cuff height, the less tendency the gasolinehas to emulsify with water. In all runs the gasoline tested was the sameexcept for the additive. The test was run on borated Z-heptadecenyl4,4-bis-(hydroxy methyl) oxazoline (additive No. A, which is the productof Example A above) and acid-treated derivatives of the same (additiveNos. 1 to 5). Additives Nos. 1 to 5 were prepared by treating additiveNo. A with different acids in an amount sufficient to furnish one moleof hydrogen per mole of borated oxazoline, and additive Nos. 1 to 3correspond to the products of Examples 1 to 3 above, respectively. Thequantity of borated 2-heptadecenyl 4,4-bis-(hydroxy methyl) oxazoline ineach gasoline was the same and was an amount to supply 0.001% by weightboron to the gasoline. The pH of each of the additives is given in Table1 to indicate the relationship of the 4 pH value of the additives tocufi height and change of hydrocarbon volume.

Table I Ml.oi Ml. of No. Additive pH Hydro- Cufi carbon Height Change ABorated 2-heptadecenyl 4,4-bis-(hy- 6.7 3 23 droxy methyl) oxazoline. 1Borated 2-heptadeccnyl 4,4-bis(hy- 5.7 --3 8 cirqxy methyl)oxazolinei-Acetic c1 2 Borated Z-heptadecenyl4,4,-bis-(liy- 4.2 0 5droxy methyl) oxazoline-l-Phosphoric Acid. 3 Borated 2-heptadecenyl4,4-bis-(hy- 3.3 2 l2 (AIQEY methyl) oxazoline-i-Oxalic c1 4 Borated2-heptadecenyl 4,4-bis-(hy- 6.6 2 22 droxy methyl) oxaZoline+Boric Acid.5 Borated 2-heptadecenyl4,4,-bis-(hy- 2.9 1 21 droxymethy'l)oxazoline+Hydrochloric Acid.

As may be seen from Table I, a smaller cutf height is noted between a pHrange of from 5.7 to 3.3. Furthermore, in Table I the hydrocarbon volumechange is indicated to be at an optimum at a pH of 4.2.

The same test was run on a series of gasoline compositions incorporatingadditives covering the same pH range provided in Table I, said additivesbeing prepared by treating borated Z-heptadecenyl 4,4-bis-(hydroxymethyl) oxazoline with varying amounts of hydrochloric acid. Theseresults are recorded in Table II below. The base gasoline was the samefor all tests and the amount of additive added to the fuel wassufiicient to supply 0.001% by weight boron to the gasoline in eachinstance.

Table II M1.of Additive pI-I Cufi Height Borated Z-heptadecenyl4,4,-bis-(hydroxy methyl) oxazoline- 6. 7 23 Borated 2heptadecenyl4,4-bis-(hydroxy methyl) oxazoline+llydrochloric Acid 4. 4 23 Do 4.0 5Dn 2.9 21

where X is selected from the group consisting of hydrogen and where R isa member selected from the group consisting of alkyl and allcenyl bothof 7-19 carbon atoms and mixtures of these as derived from naturallyoccurring fats and oils, where n is a small whole number from 1 to 3,and where R is selected from the group consisting of hydrogen and loweralkyl of 1 to 3 carbon atoms; with an acid selected from the groupconsisting of phosphoric, hydrochloric, acetic, and oxalic, in an amountso that the resulting product with phosphoric acid has a pH value ofsubstantially 4.2, with hydrochloric acid has a pH value ofsubstantially 4.0, with acetic acid has a pH value of substantially 5.7,and with oxalic acid has a pH value of substantially 3.3.

2. A method of preparing a member selected from the group consisting ofboron compounds and mixtures of said compounds for use in gasoline whichcomprises reacting a borated oxazoline compound selected from the groupconsisting of (1) ans-o N-C B-O-X Fir-0 damn-o where X is selected fromthe group consisting of hydrogen and where R is a member selected fromthe group consisting of alkyl and alkenyl both of 7-19 carbon atoms andmixtures of these as derived from naturally occurring fats and oils,where n is a small whole number from 1 to 3, and where R is selectedfrom the group consisting of hydrogen and lower alkyl of 1 to 3 carbonatoms; with an acid selected from the group consisting of phosphoric,hydrochloric, acetic, and oxalic, in an amount so that the resultingproduct with phosphoric acid has a pH value of substantially 4.2, withhydrochloric acid has a pH value of substantially 4.0, with acetic acidhas a pH value of substantially 5.7, and with oxalic acid has a pH 0value of substantially 3.3.

No references cited

1. A MEMBER SELECTED FROM THE GROUP CONSISTING OF BORON COMPOUNDS ANDMIXTURES OF SAID COMPOUND, SAID BORON COMPOUNDS BEING PREPARED BYREACTING A BORATED OXAZOLINE COMPOUND SELECTED FROM THE GROUP CONSISTINGOF (1)